Alpha, alpha-bis (4-anilino-3-nitro-benzamido)-anthraquinones



United States Patent O 3 Claims. (Cl. 260377) The present invention relates to new nitro-dyestuff pigments and a process for their manufacture.

The present invention provides nitro-dyestutf pigments of the formula in which the aryl radicals may be for example, naphthalene radicals, or more especially benzene radicals, R represents an aromatic radical, advantageously a 1:5-anthraquinonyl radical, and the benzene radicals B may contain further substituents that do not impart solubility in water.

The new dyestuffs can be obtained by condensing a halide of a carboxylic acid of the formula with an aromatic diamine in a molar ratio of 2:1.

The carboxylic acid halides of the formula (2) that are used in the process of the invention, are advantageously obtained by condensing a 3-nitro-4-halogen-benzoic acid with an arylamine, especially an aminobenzene, for example, aniline, halogenated anilines, for example, ortho-, metaor para-chloraniline, ortho-, metaor para-bromaniline, 2:5-dichloraniline, alkyl-, alkoxyor phenoxy-anilines, for example, ortho-, metaor para-methylaniline, ortho-, meta-, or para-methxy-, ethoxyor phenoxyaniline, 2:4- or 2:5-dimethylaniline or a monoacylated diaminobenzene, for example, monoacetylor monobenzoyl-paraphenylenediamine. Suitable polycyclic arylamines are 1- or 2-aminonaphthalene, para-amino-diphenyl and 3-aminopyrene. The condensation products obtained, for example, the one obtained from 3-nitro-4-halogen-benzoic acids and aniline, may be treated with halogenating agents, for example bromine.

As starting materials for the process of the invention, it is advantageous to use halides of carboxylic acids of the formula in which X X and X each represents a hydrogen atom or a halogen atom or an alkoxy, phenoxy, alkyl, phenyl or acylamino group.

Preferably, 1:5 diaminoanthraquinone is used as the aromatic diamine to be reacted with the acid halides.

HHH HHHHHHHHHHHH 3,355,693 Patented Dec. 5, 1967 There may also be mentioned, diamines of the benzene and diphenyl series, for example, those of the formula mrwG-Nm 1 B-diaminobenzene,

1 3-diamino-4-ch1orobenzene, :3-diamino-4-methylbenzene,

: 3-diamino-4-methoxybenzene, :4-diaminobenzene, :4-diamino-2-methylbenzene,

: 4-diamino-2-chlorobenzene,

4-diamino-2 S-dirnethylbenzene, :4-diamino-2-methyl-5-chlorobenzene, :4-diamino-Z-methoxybenzene, :4-diamino-2 S-dimethoxybenzene,

: 4-diamino-2 S-diethoxybenzene, :4-diamino-2 S-dichlorobenzene,

3-diamino-4 6-dinitrobenzene, :3-diamino-4: 6-dimethylbenzene,

3-diamino-4: 6-dichlorobenzene, :S-diaminonaphthalene, 4:4'-diaminodiphenyl,

3 3 -dimethoxy-4 4-diaminodiphenyl, 3 :3 -dimethyl-4 4'-diaminodiphenyl,

3 3 '-diethoxy-4 4'-diaminodiphenyl,

3 3'-dichloro-4 4-diaminodiphenyl, 2: 7-diaminodiphenylene-oxide,

1 4-diaminoanthraquinone,

1 :S-diaminoanthraquinone,

2: 6- or 2 7-diarninoanthraquinone,

2: S-diaminochrysene, 2-(4'-aminophenyl)-6-aminobenthiazole, and 2:7-diaminocarbazole.

' ingly soluble in all organic solvents and that are suitable for coloring a very Wide variety of organic products, for example, plastic substances such as caoutchouc and casein, polymerization resins for example polyvinyl chloride and copolymers thereof, polyvinyl acetals, polyethylene, polypropylene, polystyrene and the copolymers thereof with polyesters prepared from unsaturated dicarboxylic acids and diols, polyacrylates and the copolymers thereof, sili cone and silicone resins. The pigments obtained by the process of the invention are also suitable for use in the manufacture of colored condensation resins, especially aminoplasts, for example, urea-formaldehyde and melamine-formaldehyde resins, polyaddition resins for example epoxy resins, polyurethane resins and alkyd resins, and in the manufacture of colored lacquers that contain one or more of the aforementioned resins in an organic solvent, or aqueous emulsions containing one or more of the aforementioned resins or precondensates, if desired or required, in the presence of organic solvents, for example, an oil-in-water emulsion or a water-in-oil emulsion. Such emulsions are suitable mainly for impregnating or printing textiles and other sheet-like structures, for example, paper, leather and fabrics made of glass fibers, if desired or required, with subsequent curing by heat treatment. The pigments obtained by th process of the invention may also be used in the manufactur of spuncolorcd fibers, for example, fibers made of viscose, cellulose esters and polyacrylonitrile. They are also suitable for use in the manufacture of cosmetic preparations and printing inks.

The pigments, which are generally obtained from the synthesis in a form suitable for use, are advantageously converted into a finely divided state, before application. For example, the crude pigment may be ground, either in the dry state or after being moistened with water, in the presence or absence of an organic solvent and/ or a salt that can be washed out.

The pigments obtained by the process of the invention may be used either as they are as so-called toner, or in the pends on the purpose for which the preparations are ina finely divided state, the particles advantageously hav' ing a diameter not exceeding 3,u. Such preparations, which may also contain the usual additives, for example, dispersing agent or binders may be prepared in known manner by an intensive mechanical treatment, for example,

4 EXAMPLE 1 74 parts of 3 nitro 4 (4' bromophenyl)-amino benzene l carboxylic acid (obtained by brominating 3 nitro 4 phenylamino 1 carboxylic acid in glacial acetic acid), 1 part of pyridine and 27.5 parts of thionyl chloride were heated to 90 to 100 C. in 250 parts by volume of nitrobenzene, while stirring, in a round-bottomed flask provided with stirring means, a condenser and a thermometer, and maintained at that temperature for minutes, whereby the 3 nitro 4 (4-bromopheny1)-aminobenzene 1 carboxylic acid chloride that formed with the usual evolution of gas was dissolved completely. A solution of 19.6 parts of 2:5 diethoxy- 1:4-diaminobenzene in 350 parts by volume of nitrobenzene having a temperature of 90 to 100 C., was added to the solution, and precipitation occurred. The mixture was then heated to approximately 180 C., and stirred at that temperature for approximately 15 hours. After cooling the reaction mixture to room temperature, the product of the reaction was filtered off and then washed successively on the suction filter with chlorobenzone and alcohol. After recrystallization from 'y-butyrolactone, analysis gave the following figures:

Calculated: C, 51.82%; H, 3.62%; N, 10.07%; Br, 19.15%. Found: C, 52.02%; H, 3.81%; N, 10.09%; Br, 18.65%.

The product corresponds to the formula on a roller mill or in a suitable kneading apparatus. The kind of medium used, which acts as dispersing agent and which permits the intensive mechanical treatment, depends on the purpose for which the preparations are intended. For example, if it is necessary that the preparations are capable of forming a dispersion in water, sulfit'e waste liquor or salts of dinaphthylmethandisulfonic acid are used, but if they are to be used in the preparation of acetate rayon spinning solutions, cellulose acetate mixed with a small amount of solvent is used.

The favorable physical form in which the products produced according to the process of the invention are usually obtained, their chemical inertness and good thermostability enable them to be easily dispersed in the formulations and preparations of the kind defined above. It is advantageous for the dispersion to take place at a stage in the processing before the said formulations or preparations have acquired their final shape. The various shaping operations for example spinning, pressing, curing, casting or cementing, may also be carried out in the When used for the mass coloration of polyvinyl chloride, the pigment yielded yellow tints possessing a good fastness to light and a good fastness to migration.

Coloration process 5 parts of the above pigment were mixed with 95 parts of dioctyl phthalate and the mixture ground in a ball mill until the pigment was smaller than 3 0.8 part of this dioctyl phthalate paste was mixed with 13 parts of polyvinyl chloride, 7 parts of dioctyl phthalate and 0.1 part of cadmium stearate, and the mixture was then worked to and fro on a two-bowl mill for 5 minutes at 140 C. A reddish yellow foil was obtained.

By condensing 1 mol of 2:5-die'thoxy-1:4-diaminobenzone with 2 mols of the acid chlorides obtained from the condensation products of 3-nitro-4-chlorobenzene-1- carboxylic acid and the amines listed in column I of the following table by the method described in the first paragraph of this example, there are obtained pigments having the coloration properties listed in column II.

I II

The following examples illustrate the invention. Unless Aminobenzene l-amino-Z-methyl-bcnzene Colors polyvinyl chloride golden-yellow tints having a good iastness to light and a good iastness to migration.

Colors polyvinyl chloride yellow tints having a good iastness to light.

1-arnino-2:4-dimethy1benzene D 1-amino-2 S-dimethylbenzene Lamina-2: 4-dimethoxyb enzene.

When the pigment was added to a viscose spinning solution regenerated cellulose fibers were obtained that were colored yellowbrown tints possessing a goodtastness to light and good properties of wet tastness.

EXAMPLE 2 A solution of 16.8 parts of 2:5-dimethoxy-1:4-diaminobenzene in 500 parts by volume of nitrobenzene, which solution had a temperature of to C. was added to a solution of 3-nitro-4-phenylaminobenzene-l-carboxotherwise stated, the parts and percentages are by weight. 75 ylic acid chloride in nitrobenzene, which was prepared in the manner described in Example 1 from 56.8 parts In the same manner, 2 mols of 3-nitro-4-phenylaminoof 3-nitro-4-phenylaminobenzene-1-carboxylic acid, and benzene-l-carboxylic acid were condensed with 1 mol condensation was carried out for hours at about 180 of one of the aromatic diamines listed in column I of C. After cooling the reaction mixture, the product of the the following table and pigments having the coloration condensation was filtered off, washed with alcohol and 5 properties listed in column II were obtained.

I II

1. 2-methyl-5-chloro-1;4-diaminoben- Colors polyvinyl chloride brilliant yellow tints zene. possessing a good fastness to light and to migration. 2 2:5-dirnethyl-1:4-diaminobenzene. Do. 3 lz4-diamln0benzene Do. 4 1:5-diaminonaphthalene Do. 5-.-- 3:3i-d1methoxy-4:4-dlamino- Colors polyvinyl chloride reddish yellow tints diphenyl. possessing a good tastness to light and to I migration. 6 3:3 -d1chloro-4:4-diam1no- Colors polyvinyl chloride yellowish orange diphenyl. tints possessing a good iastness to light and to migration. 7 2z6-d am no-anthraquinone. o. 8 1:4-d1am1no-2-p-toluyl-sulfonyl- Colors polyvinyl chloride brilliant yellow tints benzene. possessing an excellent light fastness.

then recrystallized from -butyrolactone. Analysis gave EXAMPLE 5 the following figures. 5

Calculated: C, 62.96%; H, 4.35%; N, 12.96%. Found: By condensing 74 parts of 3-nitro-4-(4'-bromophenyl)- C, H, 457%; N 12 85% ammobenzene-l-carboxylic acid (obtained by brominat- The product corresponds to the formula. 111g 3-nitro-4-phenylamino-l-carboxylic acid in glacial HaCO When the pigment was finely dispersed in a viscose spinacetic acid) with 27.2 parts of 3:3'-diethoxy-4:4-diamining solution, the cellulosic fibers spun from the said nodiphenyl, a pigment was obtained which yielded transsolution exhibited yellow tints possessing good fastness 40 parent golden yellow tints possessing good fastness to to light and excellent properties of wet fastness. light and very good fastness to migration when used for the mass coloration of polyvinyl chloride.

Coloration place By replacing 3 nitro 4-(4-bromophenyl)-aminoben- Parts Of the Pigment obtained in the manner zene-l-carboxylic acid with 64.4 parts of 3-nitro-4-(3'- scribed in the first P g p Parts of the Sodium chlorophenyl)-aminobenzene-l-carboxylic acid (obtained Salt of 131'-diI1aPhthY1methaI1e'2IT-diSUIfOIItC acid and by condensing 3-nitro-4-chlorobenzene-l-carboxylic acid 21 Parts Of Water Were ground in one Of the kIlOWll with 3-chloraniline), a pigment was obtained which loid mills, until all Pigment Particles Were Smaller yielded yellow tints possessing good fastness to light and than In. very good fastness to migration, when used for the mass- When this aqueous pigment suspension was added to cobration f i 1 h1 id a viscose spinning solution, the conventional spinning process produced yellow cellulosic filaments. The color- 1 EXAMPLE 6 at'ion exhibited good fastness to light and very good properties of wet fastness. By condensing 63.4 parts of 3-nitro-4-(4'-methoxyphenyl)-aminobenzene-1-carboxylic acid or 80.7 parts of EXAMPLE 3 the product obtained by the monobromination of 3nitro- By condensing 80.3 parts ofthe product obtained by 4-(4'-methoxyphenyl)-aminobenzene-l-carboxylic acid in the monobromination of J3-nitro-4-(2:4'-dimethylphenglacial acetic acid with 19.8 parts of 2:7-diaminodiphenyl)-aminobenzene-l-carboxylic acid in glacial acetic acid- 'ylene oxide, pigments were obtained which yielded transor 80.7 parts of the product obtained by the monobroparent yellow tints possessing good fastness to light when mination of -D YP Y used for the mass-coloration of polyvinyl chloride. l-carboxylic acid in glacial acetic acid with 13.6 parts of 2:5-dimethyl-1:4-diaminobenzene in the manner de- EXAMPLE 7 scribed in Example 2, pigments were obtained which yielded greenish yellow tints possessing good fastness to light and very good fastness-to migration, when used for the mass coloration of polyvinyl chloride.

A solution of 10.8 parts of 1:3-diaminobenzene in 270 parts by volume of nitrobenzene was added to a solution of 3-nitro-4-phenylaminobenzene-1-carboxylic acid chloride in nitrobenzene, which was prepared in the manner EXAMPLE 4 described in Example 1 from 56.8 parts of 3-nitro-4-phen- By condensing 56.8 parts of 3-nitro-4-phenylaminobenylaminobenzene-l-carboxylic acid, and the whole was Zene-l-carboxylic acid With 17.7 parts of. 2:5-dichloro-' stirred for approximately 15 hours at approximately 180 1:4-diaminobenzene in the manner described in Exam- C. The hot yellow-brown solution was then filtered until ple 2, a pigment was obtained which yielded brilliant clear, .and the filtrate was then cooled to room temyellow tints, possessing good fastness to light and to perature. The yellow condensation product that gradualmigration, when used for the mass coloration of polyly precipitated was filtered off after some time, washed vinyl chloride. successively with chlorobenzene and alcohol, and then 7 dried in vacuo at about 100. It corresponds to the formula and then purified by stirring in boiling nitrobenzene, filtering off at about 100 C., stirring in boiling alcohol,

filtering 0d and washing with alcohol. When the condensation product had been dried, analysis gave the following figures.

Calculated: C, 54.81%; H, 2.76%; N, 9.59%; Br,

15 18.22%. Found: 0, 54.80%; H, 2.64%; N, 9.40%; Br,

The product corresponds to the formula MONHGCOH Q 1,3-diamino-4-chlorobenzene or 1,3-diarnino 4 methylbenzene pigments are obtained which also impart to polyvinyl chloride brilliant, transparent yellow tints possessing excellent fastness to light.

EXAMPLE 8 A solution of 3-nitro-4-(4-bromophenyl)-a.minobenzene-l-carboxylic acid chloride in nitrobenzene, prepared in the manner described in Example 1, was mixed with a suspension of 23.8 parts of 1:5-diarninoanthraquinone in 500 parts by volume of nitrobenzene, the whole was heated to about 180 C. and then stirred for 20 hours" at that temperature. After cooling the reaction mixture to about 100 C, the reaction product was filtered ofi When applied by the coloration process described in Example 1, the pigment colored polyvinyl chloride reddish yellow tints possessing very good fastness to light and to migration.-

When used in the spin-coloration of viscose, it yielded yellowish orange tints possessing a good fastness to light and good properties of wet fastness.

By condensing 1 mol of 1:5-diaminoanthraquinone with 2 mols of one of the acid chlorides obtained from the condensation product or 3-nitro-4-chlorobenzene-l-carboirylic acid and one of the amines listed in column I of the following table, by" the method described in the first paragraph, a pigment was obtained having the coloration properties given in column II.

I II

1.... Aminobenzene When the pigment was added to a viscose spinning solution, regenerated cellulose fibers were obtained that were colored yellowish orange tints possessing a good fastness to light and excellent properties of wet tastness.

2--.- 1-amino-3-methylbenzene Colored polyvinyl chloride yellowish orange 3. l-aminoi-methylbenzene.. Colored polyvinylchloride reddish yellow tints tints possessing a good fastness to light.

possessing good iastness to light. When the 'grnent was added to a viscose spinning solution, regenerated cellulose fibers were obtained that were colored yellowish orange tints possessing good fastness to light and excellent properties of wet fastness.

4.... 1-amino-3:E-dimethylbcnine.l--.. Colored polyvinyl chloride orange tints possessing good iastness to light.

5-... 1-amino-2-methoxybeuzene When the pigment was added to a viscose 6. l-aminoZi-methoxybenzehe spinning solution, regenerated cellulose fibers were obtained that were colored yellowish orange tintspossessing good fastness to light and excellent properties 01 wet iastness.

Do. 7--.. 1-amino4-methoxybcnzene Colored polyvinyl chloride orange tints,

8;--. 1-amino2:4-din1ethoxybenzene-... When the pigment was added to a viscose spinning solution, regenerated cellulose fibers were obtained that were colored yellowish orange tints, possessing good fastness to light and good properties of wet iastness.

9 1amino-2:4-dibromobenzene Colored polyvinyl chloride reddish yellow tints,

possessing good iastness to light. When the pigment was added to a viscose spinning solution, regenerated cellulose fibers were obtained that were colored yellowish orange tints, possessing good fastncss to light and goodproperties of wet iastncss.

9 EXAMPLE 9 A Suspension of 23.8 parts of 1:4-diaminoanthraquinone in 500 parts by volume of nitrobenzene was added to a solution of 3-nitro-4-phenylaminobenzene-l-car- 10 3-nitro-4-(4-methylphenyl)- or 3-nitro-4-(4'-methoxyphenyl)- or 3-nitro-4-(4'-bromophenyl)aminobenzene-1- carboxylic acid chloride. Furthermore, these 3 pigments produced yellowish brown tints having good fastness to boxylic acid chloride, obtained in the manner described 5 light. when incorporated into p y y chloridein Example 2, and condensation was carried out for 60 to 65 hours at about 180 C. while stirring vigorously.

What is claimed is: 1. A nitro-dyestuff pigment of the formula After cooling the reaction mixture to room temperature, the product of the condensation was filtered 01f, washed successively on the suction filter with chlorobenzene and alcohol and then recrystallized, first from nitrobenzene and then from 'y-butyrolactone. Analysis gave the following figures.

Calculated: C, 66.85%; H, 3.65%; N, 11.70%. Found: 35

When applied according to the viscose spin-coloration 45 C, 66.26%; H, 3.65%; N, 11.65%.

The product corresponded to the formula OrN 0- in which R is a,u-anthraquinonylene and X X and X 5 each represents a member selected from the group consisting of hydrogen, halogen, lower alkoxy and lower alkyl.

2. The dyestufi of the formula NHCOQNHC -B:' O NO:

3. The dyestuif of the formula C OHN- References Cited FOREIGN PATENTS 11,440 5/1911 Great Britain.

0 LORRAINE A. WEINBERGER, Primary Examiner.

H. C. WEGNER, Assistant Examiner. 

1. A NITRO-DYESTUFF PIGMENT OF THE FORMULA 